SPE 75183
New Insight on Polymer Adsorption Under High Flow Rates
G. Chauveteau, SPE, K. Denys, SPE and A. Zaitoun, SPE, Institut Français du Pétrole
Copyright 2002, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the SPE/DOE Improved Oil Recovery Symposium
held in Tulsa, Oklahoma, 13–17 April 2002.
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Abstract
In previous papers we investigated high-molecular-weight
polyacrylamide adsorption under high shear rates in low-
permeability media and found that, above a critical value γc ,
adsorbed macromolecules can reduce the permeability by
factors over hundred, suggesting a mechanism of pore throat
bridging. New lab experiments have been designed
specifically to elucidate the mechanism at the origin of this
"bridging adsorption". Polymer injections were carried out
over a wide range of shear rates in homogeneous high-
permeability granular packs having hydrodynamic pore throats
too large to be bridged by polymer macromolecules. When
polymer is injected at low shear rate (γ < γc) the adsorbed layer
thickness εHS (calculated from permeability reduction values)
does not depend on injection rate. When the injection occurs at
higher shear rates (γ > γc), εH increases slowly up to reach
maximum values εHM increasing with injection shear rate.
These εHM values were found to be large enough to explain the
very high reductions in permeability obtained previously in
low-permeability packs.
These results show that polymer adsorption in porous media
can be increased significantly by the hydrodynamic forces
normal to the pore wall, as soon as they become high enough
to "push" additional macromolecules into the already adsorbed
polymer layer. This mechanism increases both polymer
adsorption density and adsorbed layer thickness. We propose
to refer to this mechanism as a "flow-induced adsorption".
This new interpretation is consistent with all results previously
attributed to "bridging adsorption" and the new results
reported in this paper. It provides an important conceptual tool
to model polymer placement in water shutoff and to design
conformance treatment.
Introduction
In a series of previous papers,1-4 several experimental results
were presented, dealing with polymer behavior in porous
media under near-wellbore flow conditions. These
experiments showed that, when a large number of pore
volume is injected in low-to-medium permeability cores
beyond a critical shear rate γc, a plugging tendency is observed
as well as a strong increase in adsorption density.3 The
plugging does not occur either in non-adsorbing conditions or
in high permeability cores. To explain these observations, a
mechanism called "bridging adsorption" was proposed,
consisting of two steps: 1) the stretching of macromolecules
by high elongation stresses and 2) the adsorption of these
stretched macromolecules by forming numerous bridges
accross pore throats. Such a mechanism is consistent with
several observations such as:
- A rate of plugging increasing as permeability decreases.1,3
- A rate of plugging increasing with the presence of
residual oil (which reduces pore throat size).3
- A rate of plugging increasing with adsorption energy
(from neutral1,3 to cationic4 polyacrylamides).
- A rate of plugging decreasing in cores having a broad
pore size distribution.3
However, such a mechanism did not fit very well with
some other results, namely:
- The critical shear rate (around 70 s-1) is significantly
lower than the onset of coil-stretch transition ( > 200 s-1).5
- The fact that more than 99% of polymer could flow easily
(with very small apparent viscosity) through highly
bridged pore throats.
- The fact that oil could also flow easily with a very low
resistance factor, through these strongly plugged cores.
These discrepancies with the proposed mechanism of
"bridging adsorption" called for additionnal experiments. We
decided to run the same type of coreflood experiments as
before in cores with very high permeability, for which pore
throat size was too large to allow polymer bridging, even with
strongly stretched macromolecules. The experimental
procedure was designed to measure very precisely the
evolution of the thickness of the adsorbed polymer layer after
each polymer slug.
2 G. CHAUVETEAU, K. DENYS, A. ZAITOUN
Main definitions
The permeability reduction Rk induced by polymer adsorption
is defined as:
∆Ps1
Rk =
∆Ps 0
where ∆Ps1 is the pressure drop during solvent flow after
polymer adsorption at a certain flow rate Qs. ∆Ps0 is the
pressure drop during solvent flow (at Qs) before polymer
adsorption. At low flow rates, Rk is always constant
Polymer hydrodynamic adsorbed layer thickness εH can be
deduced from the measurement of Rk, assuming that the
effective or hydrodynamic pore radius Rp (Equation 5) is
reduced by an impenetrable polymer layer with thickness εH:
(
ε H = R p 1 − R k−0.25 ) (2)
The mobility reduction Rm during polymer solution flow
through a porous medium is defined as:
∆Pp
Rm =
∆Ps 0
where ∆Pp is the pressure drop during polymer solution flow
(at Qs) and ∆Ps0 is defined as above. If no other retention
mechanism than adsorption occurs, the mobility reduction Rm
depends on the bulk viscosity (as measured in a rheometer)
and the permeability reduction Rk due to adsorption, taking
into account the effects of a depleted layer on top of the
adsorbed layer.5
Since the in-situ rheological behavior of a polymer system is
usually a function of the shear rate in the porous medium, an
estimation of the effective shear rate is required. A
macroscopic description has been developed, which describes
the porous medium as a capillary bundle model with radius
Rp.6 . This leads to:
4Q α G
γ
=
(
Sφ R p − εH ) (4)
where Q is the flow rate, S is the cross-section of the pack and
φ its porosity. The geometrical factor αG , added to account for
the porous medium structure, was found equal to 2.5 for
sharp-edged grain packs.7 Note that after polymer adsorption
the shear rate increases since Rp is reduced by the adsorbed
layer thickness εH. The value of the (effective) pore radius Rp
is given by:
8k
R p = αs
φ set between the inlet and the outlet of the core to monitor the
SPE 75183
where k is the pack permeability and αs is a geometrical factor
depending on the porous medium structure. The value of αs
was found 7 to be close to 1.15 for packs of sharp-edged-grain
natural sands and SiC packs.
(1) Experimental
Brine
The brine was prepared by dissolution of 20 g/l NaCl and
400 ppm of NaN3 (bactericide and stabilizer against free-
radical depolymerization) in double distilled water. The brine
was filtered through 0.22 µm cellulose MilliporeTM
membranes and carefully degased under vacuum to avoid
bubble formation in the core.
Polymer solutions
We selected a cationic polyacrylamide used in a previous
study,4 namely APTACTM , produced by SNF Floerger. This
product, whose chemical structure is given in Fig. 1, was
shown to be very stable in our experimental conditions. It
contains 12% of cationic groups. Its molecular weight is 6 x
106 daltons, giving a value of polymer coil diameter in
solution of around 0.3 µm. The polymer was dissolved in the
brine at a concentration of 360 ppm. To remove microgels, the
(3) polymer solution was filtered at very low shear rate (Q = 6
ml/h) through a set of MilliporeTM membranes (diameter 12
cm, pore diameter 8, 3 and 1.2 µm placed in series). The
viscosity was 1.50 mPas at 30°C, yielding a relative viscosity
ηr = 1.84.
Porous media
As in previous experiments, we choose model porous media
made of packs of silicon carbide (SiC) grains. Such a material
is available at several grain sizes, each one with a narrow size
distribution. Its shape and surface properties8 are comparable
to that of natural sands. For our experiments we used 110-µm
SiC grains, giving packs with a permeability of around 5.3×10-
12
m2. Before packing, the SiC grains were submitted to
several washes under ultrasonics to remove impurities. The
SiC packs had a diameter of 1.50 cm and a length of about
3cm. The pore volume was around 2.1 cm3. We used small
cores in order to inject a large number of pore volumes and
thus simulate near-wellbore conditions. The SiC packs were
made by dry packing SiC grains in a glass core holder. Since
the grain distribution is narrow, the pore structure is rather
homogeneous and was quantitatively described by the Grain
and Pore Throat model.9,10 Table 1 summarizes SiC pack
characteristics.
Coreflood set-up and procedures
The coreflood set-up consisted of a constant flow rate piston-
type pump, a core and a fraction collector, all placed in series.
The core was immersed in a water bath thermostated at 30°C.
Differential pressure transducers (0-15 and 0-300 mbar) were
(5)
SPE 75183 NEW INSIGHT ON POLYMER ADSORPTION UNDER HIGH FLOW RATES
pressure drop during injection. The data were recorded on
a computer.
The procedure used for the coreflood experiments consisted
in injecting successive large slugs of polymer solution
separated by brine slugs to wash out non-adsorbed polymer.
The injections started at the lowest flow rate of 1 ml/hr, and
then the rate was increased step by step. The pressure drop
was monitored continuously during both polymer and brine
injection. Plots of the mobility reduction Rm (Equation 3) and
the permeability reduction Rk (Equation 1) vs. the number of
injected pore volumes were established from pressure drop
measurements. During each brine injection, the flow rate was
varied in order to obtain the Rk curve vs. shear rate. The
thickness of the adsorbed polymer layer εH was determined
from Rk measurements, using Equation (2).
Two coreflood experiments were performed with very similar
packs ( See Table 1). The first one consisted of two polymer
slugs injected at different rates and separated by brine slugs.
The second one involved 6 large polymer slugs injected at
shear rates ranging between 17 and 544 s-1, also separated by
large brine slugs.
Results and Discussion
In the first pack, we injected two large polymer slugs
separated by brine slugs, the first one at a shear rate of 136 s-1
and the second one at a shear rate of 204 s-1. In both cases, the
mobility reduction Rm increased vs. time (Fig. 2), showing an
unexpected unsteady-state behavior that cannot be explained
by the "bridging adsorption" hypothesis for two reasons: 1) the
shear rates are too small to induce a coil-stretch transition and
2) the pore throat sizes are too large to be bridged, even by
strongly stretched polymer macromolecules.
This first observation led us to run a second coreflood in a
much broader range of shear rates, starting from a very low
shear rate (17 s-1) to ensure that adsorption occurred under
static conditions, i.e. without any additional force other than
that due to Brownian motion. Then the injection flow rate was
increased systematically by a factor 2 (34, 68 136, 272 and
544 s-1). During the 3 last polymer injections, we observed a
progressive increase in mobility reduction Rm up to reach
stable values after injection of a large number of pore volume
of polymer solution. Table 2 summarizes all experimental
results, i.e., Rm, Rk as well as polymer layer thickness vs.
shear rate.
Fig. 3 gives the plot of the stabilized Rm as a function of the
shear rate maintained during polymer slug injection. At the
lowest rates, Rm is almost constant (Rm ~ 2.3). It starts to
increase above 50 s-1 and reaches a value as high as Rm = 11.7
at 544 s-1.
The permeability reduction Rk curves vs. shear rate, obtained
after each polymer injection show the same trend (Fig. 4). The
Rk value remains constant at the lowest shear rates and then
increases as the shear rate increases, with an onset around
100 s-1.
3
From the Rk values measured under low shear rate conditions
where the thickness of adsorbed layer is not affected by
hydrodynamic forces, we calculated the maximum εH values
resulting from polymer injections at increasing shear rates, and
plotted them on Fig. 5. The plot shows the existence of two
different adsorption regimes. When the polymer solution is
injected at low shear rate, the adsorbed layer thickness is
constant (εHS ≈ 0.65 µm) and equal to the value previously
obtained in low-permeability packs.4 Above a critical shear
rate of around 70 s-1, we enter a new regime where the
adsorbed layer thickness increases strongly with the rate of
polymer injection up to reach a maximum value
approximately 3 times larger, εHM = 1.8 µm.
All these results lead us to propose a new mechanism of
polymer adsorption under high flow rates. Since, because of
the very large pore size, pore bridging is not possible in our
experimental conditions, the increase in Rk must be attributed
to an increase in polymer layer thickness εH. This increase is
clearly related to the increase in shear rate, thus to
hydrodynamic forces applied on polymer macromolecules
close to pore wall. At low rate, εH remains constant as
expected when the hydrodynamic forces are too small to affect
macromolecule conformation, so that polymer adsorbs as
under "static" conditions. It must be noted that, under this
"static adsorption" regime, only the attachment step is "static",
but the kinetics of adsorption depends on convection as
described in details for the deposition of colloidal particles.11
In this regime, when adsorption energy is low, the thickness is
close to the diameter of the polymer coil in bulk solution.5
When adsorption energy is high, as expected for the cationic
polymer used in this study, εH is expected to be larger than
coil diameter in solution. But whatever the adsorption energy
is, we expect εH to be constant, with the polymer covering
homogeneously the surface of the pores. Above 50 s-1, an
additional adsorption occurs whose magnitude increases with
hydrodynamic forces. In this "flow-induced adsorption"
regime, the hydrodynamic forces favors the penetration of
new macromolecules inside the "static adsorption" layer
despite the existing osmotic barrier. Thus, the density of
adsorbed macromolecules increases. The zones of the pore
surface where hydrodynamic forces are the highest are located
at the entrance of pore throats, where polymer adsorption has
a strong effect on permeability reduction.
Fig. 6 gives a picture of this "flow-induced adsorption"
mechanism. Although pore bridging by macromolecule
adsorption remains a possibility, more especially in the
smallest pore throats, the new mechanism better fits with the
three observations suggesting doubts about the "bridging
adsorption" hypothesis, namely, the low value of the onset
shear rate and the weak resistance caused by this "bridging"
adsorption to macromolecule propagation and to oil flow. The
"flow induced adsorption" mechanism remains also totally
consistent with the other observations such as the very high
mobility reduction and permeability reduction values obtained
in low-permeability media (an adsorbed layer with a thickness
4 G. CHAUVETEAU, K. DENYS, A. ZAITOUN
of 1.6 µm is expected to plug a 100 mD core completely) and
the absence of plugging when polymer adsorption is inhibited.
Obviously, more experimental data are required to better
describe this mechanism, which looks very favorable for water
shutoff and conformance control applications. Indeed, the
hypothesis of the formation of a thicker adsorbed polymer
layer allows to understand how polymer penetration in low-
permeability zones can be very strongly reduced without
affecting significantly oil permeability.
Conclusions
1. A new regime of polymer adsorption occuring under
near-wellbore flow conditions, called "flow-induced
adsorption" is proposed.
2. "Flow-induced adsorption" of polymer in porous
media results from the effects of hydrodynamic forces
becoming large enough to push additional
macromolecules over the osmotic energy barrier due
to "static adsorption" polymer layer.
3. This "flow-induced polymer adsorption" mechanism
has been elucidated from coreflood data obtained
during injection of cationic polyacrylamide solutions
into well-characterized model granular packs having
pore throats too large to be bridged by polymer.
4. This "shear-induced adsorption" mechanism is
consistent with all available experimental results
previously interpreted by the "bridging adsorption"
theory, including the easy propagation.of polymer
macromolecules and the low reduction in oil
permeability, even when water permeability is divided
by a factor of 100 and more..
5. Further experimental data are required for a
quantitative modelling of this "shear-induced
adsorption", which may play a major role in water
shutoff and conformance control applications.
Nomenclature
Rk = Permeability reduction
Rm = Mobility reduction
∆Ps0 = Pressure drop during solvent flow before
polymer adsorption (at a certain flow rate
Qs) [kg/ms2]
∆Ps1 = Pressure drop during solvent flow (at Qs)
after polymer adsorption [kg/ms2]
∆Pp = Pressure drop during polymer solution flow
(at Qs) [kg/ms2]
εH = Hydrodynamic adsorbed layer thickness [m]
εHM = Maximum adsorbed layer thickness [m]
SPE 75183
εHS = Static adsorbed layer thickness [m]Rp
= Mean pore radius [m]
Q = Flow rate [m3/s]
S = Cross-section of the porous medium [m2]
φ = Porous medium porosity
αG = Shear rate geometrical factor
k = Permeability [m2 or D ≈ 0.98 x 10-12 m2]
αS = Pore throat geometrical factor
ηr = Relative viscosity (ratio of viscosity
polymer
solution and viscosity solvent)
-1
γ
= Shear rate [s ]
-1
γ
c = Critical shear rate [s ]
References
1. P. Zitha, G. Chauveteau and A. Zaitoun, "Permeability
Dependent Propagation of Polyacrylamides Under Near-
Wellbore Flow Conditions", SPE 28955 presented at the 1995
SPE International Symposium on Oilfield Chemistry, San
Antonio, February 14-17
2. P. Zitha and C. Botermans, "Bridging Adsorption of Flexible
Polymers in Low-Permeability Porous Media", SPE 36665
presented at the 1996 SPE Annual Technical Conference and
Exhibition, Denver, October 6-9
3. A. Zaitoun and G. Chauveteau, "Effect of Pore Structure and
Residual Oil on Polymer Bridging Adsorption", SPE 39674
presented at the 1998 SPE/DOE Improved Oil recovery
Symposium, Tulsa, April 19-22
4. K. Denys, C. Fichen and A. Zaitoun, "Bridging Adsorption of
Cationic Polyacrylamides in Porous Media," SPE 64984
presented at the 2001 SPE International Symposium on Oilfield
Chemistry, Houston, TX, 13-16 February.
5. G. Chauveteau and K. Sorbie, "Mobility Control by Polymers in
Basic Concepts in Oil Recovery Processes", Ed. Marc Baviere,
Elsevier (1991).
6. A. Zaitoun and N. Kohler, "Two-Phase Flow Through Porous
Media: Effect of an Adsorbed Polymer Layer," SPE 18085
presented at the 1988 SPE Annual Technical Conference and
Exhibition, Houston, TX, October 2-5.
7. G. Chauveteau, "Rodlike Polymer Solution Flow through Fine
Pores: Influence of Pore Size on Rheological Behaviour", J. of
Rheology 26, 111 (1982).
8. Médout-Marère V., EL Ghazaoui A., Charnay C., Douillard
J.M., Chauveteau G. and Partyka S.: “ Surface Heterogeneity of
Passively Oxidized Silicon Carbide Particles : Hydrophobic-
Hydrophilic Partition” J.Coll. Int. Sc., April 2000.
9. Chauveteau G., Nabzar L., El Attar Y. and Jacquin C.: “Pore
Structure and Hydrodynamics in Sandstones”, SCA 9607,
International Symposium of the Society of Core Analysts,
Montpellier, France, 8-10 September, 1996.
10. G. Chauveteau, "The Grain and Pore Throat Model: A Tool to
Predict Mass Transport and Formation Damages", SPE 73736
to be presented at the Int. Symp.on Formation Damage Control,
Lafayette, Louisiana, 20 Feb. 2002.
11. Chauveteau G., Nabzar L. and Coste J. P.: “Physics and
Modeling of Permeability Damage Induced by Particle
Deposition”, SPE 39463, SPE International Symposium on
SPE 75183 NEW INSIGHT ON POLYMER ADSORPTION UNDER HIGH FLOW RATES 5

Formation Damage Control, Lafayette, Louisiana, 18-19

February 1998.

Acknowledgements
The authors would like to acknowledge the European Union
Commission for the funding of this work, Michel Renard for his
determining contribution to the experimental work and W.B. Russel
for very helpful discussions.

Table 1: Main characteristics of the two 110 µm SiC packs

Experiment Permeability k Porosity φ Pore volume PV Core length

(10-12 m2) (cm3) (cm)
1 5.27 0.38 2.10 3.15
2 5.34 0.38 2.12 3.15

Table 2 : Mobility and permeability reductions after polymer injections at different flow
rates (ml/h) and shear rates ( s-1 )

Flow rate during Rm Rk Rk Rk Rk Rk

polymer injection (at 5 ml/h) (at 10 ml/h) (at 20 ml/h) (at 40 ml/h) (at 80 ml/h)
(ml/h) ( s-1 ) (17s-1) (34 s-1) (68 s-1) (136 s-1) (272 s-1)
5 17 2.16 1.25 1.26 1.29 1.42 1.84
10 34 2.25 1.29 1.28 1.32 1.42 1.86
20 68 2.42 1.32 1.31 1.32 1.41 1.80
40 136 2.98 1.40 1.39 1.39 1.47 2.13
80 272 4.33 1.54 1.51 1.51 1.69 1.92
160 544 11.70 1.71 1.70 1.67 1.86 2.88

CH2 CH CH2 CH

C O C O

NH2 1-p NH p

(CH2) 3
+
CH3 N CH3
TM
APTAC CH3

Fig. 1: The molecular structure of polymer APTACTM

6 G. CHAUVETEAU, K. DENYS, A. ZAITOUN SPE 75183

3 14

Mobility Reduction at Equilibrium

Mobility and Permeability Reduction

12

10

8
2
6

Polymer Brine Polymer Brine 2

136 s-1 136 s-1 204 s-1 136 s-1
1 0
0 100 200 300 400 500 600 10 100 1000
Pore Volume Injected Applied Shear Rate , γ (s-1)

Fig 2 : The adsorption from a polymer solution injected at high shear Fig 3 : The maximum mobility reduction reached at equilibrium
rates leads to a slow but significant increase in mobility reduction, increases as the applied shear rate increases.
with a tendency towards stabilization.

3 2

Shear Rate during Adsorption :

Thickness at Equilibrium (µm)

17 34 68 270 540
Permeability Reduction

Adsorbed Layer

2 1

Static Adsorption Flow-Induced Adsorption

R egim e γa* R egim e

1 0
10 100 1000 10 100 1000
-1
Shear Rate , γ (s ) Shear Rate Applied during Adsorption , γ a (s -1 )

Fig.4 : The onset of the shear thickening of adsorbed layer (γ*≅100s-1) Fig.5 : The transition between static and flow-induced adsorption
indicates when hydrodynamic forces become high enough to regimes is smooth and occurs at a critical shear rate γc
affect the conformation of adsorbed polymer.

Fig.6 : A schematic picture showing in the upper part (A) the polymer adsorbed from a solution injected in the"static" regime and in the lower
part (B) the larger adsorbed layer resulting from the effects of hydrodynamic forces which induce an increase in adsorption density and in
adsorbed layer thickness.